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Advanced Geochemistry of Natural Waters

by: June Gottlieb

Advanced Geochemistry of Natural Waters GEOL 578

Marketplace > University of Idaho > Geology > GEOL 578 > Advanced Geochemistry of Natural Waters
June Gottlieb
GPA 3.52

Scott Wood

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Scott Wood
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This 13 page Class Notes was uploaded by June Gottlieb on Friday October 23, 2015. The Class Notes belongs to GEOL 578 at University of Idaho taught by Scott Wood in Fall. Since its upload, it has received 46 views. For similar materials see /class/227864/geol-578-university-of-idaho in Geology at University of Idaho.


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Date Created: 10/23/15
LESSON 2 ACIDBASE CHEMISTRY MODULE 5b AcidBase Titrations and pH Buffers Start Audio Lecture 650L573 Anv anceu Geochemistry of Natural Waters Titration of a strong acid with strong base at va riiqus cqnicentratigns 9f acid and base NaOH ml 2 GEOL57S Advanced Gauchemis try of Natural Waters lTitratiion of a strong base with strong acid HCI m 1 5mm AMA Adkmwmxmmm tion of weak acids with strong base um mu w my WMRMWMMWW Buffer region in titration urves u hwwnlunw mum Wu mm Mvnhul mm a Wm um 41 0 m an mm M m w In 5 mm 9 mwmmmm v Titration of a weak acid with strong base in pgsgnce ofjndicrat Methyl red transition range I I orange range 80 100 120 140 160 950L578 Advanced Geochemistry of Natural Waters What can titrations tell us 0 Concentration of acid or base present analysis 0 pK of acid or base present thermodynamics Titration of mixtures of acids or bases If the pK s are sufficiently different the stronger acid base will be titrated first then weaker acid base We will be able to see two or more breaks in titration curve ie equivalence points if ApK z 4 or more Same rule applies for polyprotic acids n l Ili PKA GEOL57S Advanced Gauchemistry of Natural Waters Titration of a mixture of weak acids with a strong base 388 swim Ma mammwmmimm Titration Dfa mixture of weak and strong acids with a strong base 1 j Advanced Geochemistry of Natural Waters LESSON 4 itation and Dissolution MODULE 4a So ubmtv of Carbonate Mmera s Start Audio Lecture gotsumamcamswmwo Ms SOLUBILITV 0F CARBONATES dosed Svstem a CT ts constant wnat ts tne maximu concentratton as a tonctton of CTan 35 239 Km 2 Ca KSoCOJ39 KscCruz 12 known as a mnctton opr so tnts eooatton we ds m dwsso ved Ca2 d DH7 Where pH gt pK2 for Hzcog a a 1 o and C c0321 So ubmtv 5 controHed ov the above eooatton and ts pHnndeoendent ammo Ma Nehemqu MNAurIA w wnere pK lt pH lt pKZ too 1 o and C H0037 CaCOJG W e Ca2 H00 2 log K logE Ca 16031 K oo 03 mg c pH so s npe ufp utu ug 031 vs on w tn 5 s npe om Where on lt pK lt on w 1 o and c caco s 2w H Ca Caz39H 60 log K 1ng logKlogCa2log CTZpH 3 s ch039 H co gure 5 5 mm Slumm at Murgzn Sulubxhly or funcnun epr Dashed pumuns of curves are memstable gammamcamwmmw Mm DISSOLUTION 0F CALCITE IN PURE WATER soeoes Ca2 hzcog HCOJ39 c0327 H OH39 Mass aetroh expressions on pKZ pKSu pKw Mass ba ance ov storehrorhetrv Ca2 c Hews Hcos391 cor E ectroneutrahtv 2 1 H HCOJ39 2Colzr OH39 From the so ubihtv product We e Ca2 Kenc0327 cor Cruz Hcos39 Cray H2603 Cram ammo Ma anthemqu Wm WM Ca2 Kenweer but ca2 cT so 552 Cr M12 503239 2K5Du2uz39 HCOa39 K50 2U2r H2503 KsD 2 2 how subsutute mto the charge ba a ce 2K50 2U2 W 1KsDW2 2 2KseUe KwW KenU2 22 1 202 W KwW 0 S e et l GEDL578 Advanced Geochemistry ofNatul39al Waters GRAPHICAL SOLUTION T0 SOLU B39ILITY 0F LgALCITE INl PURE ATER Start with charge balance 2Ca2 H HCO339 2CO3239 OH39 Because calcite is a base OH39 gtgt H and HZCO3 is negligible so CT Ca2 e HCO339 CO3239 and 2Ca2 Ca2 CO3239 OH39 Ca2 CO3239 OH39 For calcite CO3239 is almost negligible but for other more insoluble carbonates it is negligible so Ca2 m 0H Figure 5 6 from Stumm amp Morgan Solubility of metal carbonates in a closed system in pure water Me2 CT Dashed portions are metastable l GEDL578 Advanced Geochemistry of Natural Waters l DISSOLUTION 0F CALCITE IN A SOLUTION LD F 51349115135199 KiBASE All equations are same as in previous example but must modify the charge balance to CA CB Ksoocz122 01 202 H KW solve the above for pH by trial and error and then 032 CT Kw0 2 2 C03239 0c2Kso0cz12 HCO339 a1Ksooc212 HZCO3 ocoKsooc212 V i Advanced Geochemistry of Natural Waters LESSON 2 ACIDBASE CHEMISTRY MODULE 5c Add Base T trat ons and pH Butters Start Audio Lecture wwwmacamewmmw Ma BUFFER INTENSITY A measu mtenswty butter capac tv womd be the mverse of the 5 0pe of the txttatxon curve at Buffer intensitv re of the butter t anv pom dog if dCA 7 de de For a monoprotwc system recang that Ca C Or391 H dCE iCdad0H idH deide de de 3 came Ma laminarqu Wm WM iw 23025H de 712 3ozsd1nH dH H L 2302301117 de 123025d1n011 d dH da Zgozsc KAH KAHH DZ 070 am am dH HFL a H Kan l U KNIH D 23025HA A C Ci 23025auac d pH 6 23025H0H szzzn H4 A 6 7 23025H 0H HAD1A7J The mammum buffer intensity mm at the m emnn pmnt nfthe mum curve nrwhere d2 a 7 0 MPH2 Tm Enndmnn uncurs where U1 a PIN A Snluhnn 15 well buffered atthreepmnts when H 15 dummant4 AnrpHpKA Wham n A 1 7 v V 7 I m 1 mm r w Fxgure 3 10am 39nm Stumm and Mnrgan M 7x10 gure 10d 39nm smmm and Mnrgan 39 sicmm cialmsiq MIurMis uquot BU ER INTEN SITV FUR MIXTURES 0F ACIDS 6 23025H OH CAaHAaA CBaHBaB 23025H 0HHfimfi HA VIA 1731 3 NZ302511 OH39 HzcnHCV HCVCZV K Hzc 1HC C39C239 The above is valid as long as KMKZ gt 100 mum mmecamssq MNtmrA Mes 39GRAPHICAL DETERMINATION OF BUFFER JNTENSIIV n 23m5H390HWI K HA PM 1 At pH lt pKA HAD HAD 50 ps 2 3H OH39 A39 AtpH gt DKA HAD w 50 M 2 3H OH39 HADD Thus buffer inten v can be ca cu ated from a specwatwon dwagram bv summmg aH concentrations represented bv a hne ofsxope 1 and mumpwmg bv 2 3025 i am Advanced Geochemistry of Natural Waters Aqueous Complexes Coordination Chemistry Start Audio Lecture gunmamcamwmmw we THE CHELA TE EFFECT o Multidentate ligands are much stronger meme Wm W C HELATE r came and WHAT IS THE CAUSE OF THE EFFECT G 7 TA For mahv hgahds AH rs about the same m muxtr and monordentate comp exes but there rs a arger entropy mcrease upon cheTatrow 110 120 4w 9 CLAN 13 4H20 110 120 N e CLAN 4H20 The second reactron resmts m a greater mcrease in A8 Figure 511 r 4Cuu nu DH8 v No COMPLEX HEMHZCHZNHZ 390 ruchnchzNNcHz 12 39039 l I I w I o0 loquot 1039 loquot Ioquot 3 10 5 ID Cull I 4 73 Figure 612a from lt FEUIDT 10 M nocardamine St Morgan LT 10 M Complexmg ofFeIII F 15 quot A The degree of Lil 7 DCTA complexation is EDTA expressed as ApFe for i 12 f various ligands at a 3 concentration of 1039Z D I oxalate F M The complexmg m 3 39 citrate 9 effect 15 highly pH 5 r110 dependent because of 39 39 V 5 the competing effects of a 4 H an O 39 oW and 0 high pH respectively Fe39 F23 JZ FeOHW 5 Figure 612b from Sturmn amp Morgan Chelation of ZnII 1 LT10395 MgtZnT 0 25 c01 2 citrate 5 6 7 8 9 pH ApZn log ZnTZn39 m Icollnate nocardamine nitn39oltriacetate ulvic acid Gawain 4111mm 1311115 METAL ION BUFFERS Ana ogous to pH buffer Conaden Me Le MeL Me KMeL L It We add MeL and L m approximatew equa quantmes Me Mu be ma ta1ned approxnnatew constant uness a otaddmona meta or Hgand is ad arge amount ded 1t MeL L tnen pMe pw 10157 a mew Mp1 Wee Examp e Ce EDTA Y white 031 Ufa semen Mtn tne mmpusmun e v e 1 gsx1u1MCe g szmlM pH 5 13 and 1 e u 1 M 2D0c Fur EDTA DK 2 EIpK1 2 E71pK 5 15 and pK 1m 25 cm2 Ca w 7 m CdHY Kan 10 CaonHyze 1 Ca Ca CaY2 CaHx KW103 Ca2l1 meh KWK H HY lama Game 11 Nemmulw 1111111 W412 11 14rmquot1Hyszi39HYquot1quotCayz39CaH139 Yquotlta39gtquot Ca 1Yquot1Ilt1y0a H JIMWW 17 m Jew LHif ZWH K K we K1199 1sz 1 Equaunns 1 and 11 mustbe snlved mm and ennr We knnw pH Sn we can calculate ud11eeuy We can then assume that Yr a1 salve 1 11 Car Th1 appmachleads m cm M CaHY109x10 eusmv M HEY 8 zmut M H 1 9 6611103 MCa7 412x105MY x 05MH2Y788x103MHY 2261110314 9


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